Serpentinites release at sub-arc depths volatiles and several fluid-mobile trace elements found in arc magmas. Constraining element uptake in these rocks and defining the trace element composition of ...fluids released upon serpentinite dehydration can improve our understanding of mass transfer across subduction zones and to volcanic arcs. The eclogite-facies garnet metaperidotite and chlorite harzburgite bodies embedded in paragneiss of the subduction melange from Cima di Gagnone derive from serpentinized peridotite protoliths and are unique examples of ultramafic rocks that experienced subduction metasomatism and devolatilization. In these rocks, metamorphic olivine and garnet trap polyphase inclusions representing the fluid released during high-pressure breakdown of antigorite and chlorite. Combining major element mapping and laser-ablation ICP-MS bulk inclusion analysis, we characterize the mineral content of polyphase inclusions and quantify the fluid composition. Silicates, Cl-bearing phases, sulphides, carbonates, and oxides document post-entrapment mineral growth in the inclusions starting immediately after fluid entrapment.
Compositional data reveal the presence of two different fluid types. The first (type A) records a fluid prominently enriched in fluid-mobile elements, with Cl, Cs, Pb, As, Sb concentrations up to 103 PM (primitive mantle), ∼102 PM Tl, Ba, while Rb, B, Sr, Li, U concentrations are of the order of 101 PM, and alkalis are ∼2 PM. The second fluid (type B) has considerably lower fluid-mobile element enrichments, but its enrichment patterns are comparable to type A fluid.
Our data reveal multistage fluid uptake in these peridotite bodies, including selective element enrichment during seafloor alteration, followed by fluid–rock interaction along with subduction metamorphism in the plate interface melange. Here, infiltration of sediment-equilibrated fluid produced significant enrichment of the serpentinites in As, Sb, B, Pb, an enriched trace element pattern that was then transferred to the fluid released at greater depth upon serpentine dehydration (type A fluid). The type B fluid hosted by garnet may record the composition of the chlorite breakdown fluid released at even greater depth.
The Gagnone study-case demonstrates that serpentinized peridotites acquire water and fluid-mobile elements during ocean floor hydration and through exchange with sediment-equilibrated fluids in the early subduction stages. Subsequent antigorite devolatilization at subarc depths delivers aqueous fluids to the mantle wedge that can be prominently enriched in sediment-derived components, potentially triggering arc magmatism without the need of concomitant dehydration/melting of metasediments or altered oceanic crust.
•The Gagnone metaperidotites record multistage subduction metasomatism and dehydration.•They trap inclusions of fluids evolved during breakdown of antigorite and of chlorite.•The trace element compositions of such fluids indicate recycling of sedimentary components.•Altered subduction-zone mantle uptakes and delivers sediment-derived elements to fluids.•This transfer process may not require concomitant subarc dehydration of slab metasediment.
An efficient, clean procedure for the measurement of element mass fractions in bulk rock nanoparticulate pressed powder pellets (PPPs) by 193 nm laser ablation ICP‐MS is presented. Samples were ...pulverised by wet milling and pelletised with microcrystalline cellulose as a binder, allowing non‐cohesive materials such as quartz or ceramics to be processed. The LA‐ICP‐MS PPP analytical procedure was optimised and evaluated using six different geological reference materials (JP‐1, UB‐N, BCR‐2, GSP‐2, OKUM and MUH‐1), with rigorous procedural blank quantification employing synthetic quartz. Measurement trueness of the procedure was equivalent to that achieved by solution ICP‐MS and LA‐ICP‐MS analysis of glass. The measurement repeatability was as low as 0.5–2% (1s, n = 6) and, accordingly, PPP homogeneity could be demonstrated. Calibration based on the reference glasses NIST SRM 610, NIST SRM 612, BCR‐2G and GSD‐1G revealed matrix effects for glass and PPP measurement with NIST SRM 61×; using basalt glasses eliminated this problem. Most significantly, trace elements not commonly measured (flux elements Li, B; chalcophile elements As, Sb, Tl, In, Bi) could be quantified. The PPP‐LA‐ICP‐MS method overcomes common problems and limitations in analytical geochemistry and thus represents an efficient and accurate alternative for bulk rock analysis.
Key Points
Clean and efficient analytical procedure that allows the quantification of up to 58 elements, including unconventional geochemical tracers such as B, As, Sb, Tl and Bi.
Measurement trueness equal to that of solution ICP‐MS and LA‐ICP‐MS measurement of glass.
Elemental fractionation employing NIST SRM 61× glasses as calibrator is observed, the use of basalt glasses (e.g., BCR‐2G, GSD‐1G) eliminates the problem.
To contribute to our understanding of the mechanisms and pathways of fluid movement through deeply subducted crust, we investigate high-pressure veins cutting eclogite-facies (∼2·0 GPa and ∼600°C) ...metagabbros of the Monviso Ophiolite, Italian Western Alps. The veins consist mainly of omphacite with minor garnet, rutile, talc and accessory zircon. Most of the vein minerals have major and trace element compositions that are comparable with the host-rock minerals, and vein and host-rock zircons have similar Hf isotopic compositions. These observations support the conclusions of previous studies that these veins largely formed from a locally sourced hydrous fluid during prograde or peak metamorphism. However, the bulk-rock Cr and Ni contents of the veins are significantly higher than those of the surrounding host eclogites. We also document distinct Cr-rich (up to weight per cent levels) zones in omphacite, garnet and rutile in some vein samples. Vein garnet and talc also have relatively high MgO and Ni contents. X-ray maps of vein garnet and rutile grains reveal complex internal zoning features, which are largely defined by micrometre-scale variations in Cr content. Some grains have concentric and oscillatory zoning in Cr, whereas others feature a chaotic fracture-like pattern. These Cr-rich zones are associated with high concentrations of Ni, B, As, Sb, Nb, Zr and high ratios of light rare earth elements (LREE) to middle REE (MREE) compared with low-Cr vein and host-rock minerals. Petrological and mass-balance constraints verify that the Cr-rich zones in the veins were not derived from internally sourced fluids, but represent precipitates from an external fluid. The external source that is consistent with the distinctive trace element characteristics of the vein components is antigorite serpentinite, which forms the structural basement of the high-pressure metagabbros. We propose at least two separate growth mechanisms for the Monviso veins. Most vein infillings were formed during progressive prograde metamorphism from locally derived fluid. Influx of the serpentinite-derived or other external fluid was transient and episodic and was probably achieved via brittle fractures, which preferentially formed along the pre-existing vein structures. The dehydration of serpentinite at high pressures in subduction zones may provide crucial volatiles and trace elements for arc magmas. Our results indicate that the movement of these fluids through subducted oceanic crust is likely to be highly channeled and transient so the progressive development of vein systems in mafic rocks may also be crucial for forming channelways for long-distance fluid flow at depth in subduction zones.
The Erro Tobbio olivine-antigorite serpentinites and associated dehydration veins represent hydrated oceanic mantle rocks that escaped complete dehydration and recycling into the mantle after ...subduction to ~ 550–600 °C and 2.0–2.5 GPa. These rocks thus offer valuable insights into the petrological evolution of a slice of hydrated oceanic mantle and the geochemical cycling down to intermediate subduction zone depths. Our study emphasises the role of brucite upon rock-buffered hydration and subduction dehydration employing bulk and in situ chemical data sets combined with petrology.
Bulk rock data reveal a coherent mantle peridotite slice affected by variable melt depletion and refertilisation. Subsequent fluid-rock interaction stages proceeded isochemically with respect to SiO2, i.e., without significant SiO2 enrichment characteristic for hydrothermal ocean floor serpentinisation. Relicts of low-T mesh textures after olivine and preservation of precursor mineral and low-T hydration geochemical features indicate a lack of subsequent fluid and metamorphic overprinting, even on scales of tens of micrometres. Fluid-mobile element enrichments are modest with exceptions for B and W. Enrichment signatures of U/Cs < 1 and Rb/Cs of 4–26 are characteristic of shallow forearc hydration within or atop the slab by fluids derived from breakdown of clays or first dehydration of altered oceanic crust with a subordinate sedimentary pore fluid component. Overall, the geochemical and petrological changes of the Erro Tobbio peridotites during fluid-rock interactions were rock-buffered, in contrast to fluid-buffered hydration accompanied with significant SiO2 metasomatism at, e.g., mid ocean ridges.
Silica-neutral rock-buffered serpentinisation resulted in prominent brucite formation upon olivine hydration. In absence of excess SiO2, subsequent serpentine transformation of chrysotile/lizardite to antigorite likely produced even more brucite. Rock-buffered fluid-rock interactions thus provide a mechanism for stabilising brucite in subduction zone serpentinites, presumably along hydration fronts and within deeper sections of the oceanic lithospheric mantle. Finally, brucite + antigorite dehydration produced up to 40 vol% of metamorphic olivine and prominent olivine + Ti-clinohumite + magnetite vein networks at temperatures <550–600 °C, prior to complete antigorite breakdown. Wall rocks released alkali elements, B, Cr, As, Sb, and Ba into the dehydration fluids, along with substantial Sr, REE and HFSE redistribution into vein minerals.
Display omitted
•Olivine antigorite serpentinites record rock-buffered (de-)hydration histories.•Brucite is central to water and element cycling during forearc dehydration.•Rock-buffered serpentinisation limits SiO2 metasomatism, favouring high brucite modes.
Analyses of co-existing silicate melt and fluid inclusions, entrapped in quartz crystals in volatile saturated magmatic systems, allowed direct quantitative determination of fluid/melt partition ...coefficients. Investigations of various granitic systems (peralkaline to peraluminous in composition, log
fO
2
=
NNO−1.7 to NNO+4.5) exsolving fluids with various chlorinities (1–14
mol/kg) allowed us to assess the effect of these variables on the fluid/melt partition coefficients (
D). Partition coefficients for Pb, Zn, Ag and Fe show a nearly linear increase with the chlorinity of these fluid (
D
Pb
∼
6
∗
m
Cl,
D
Zn
∼
8
∗
m
Cl,
D
Ag
∼
4
∗
m
Cl,
D
Fe
∼
1.4
∗
m
Cl, where
m
Cl is the molinity of Cl). This suggests that these metals are dissolved primarily as Cl-complexes and neither oxygen fugacity nor the composition of the melt affects significantly their fluid/melt partitioning. By contrast, partition coefficients for Mo, B, As, Sb and Bi are highest in low salinity (1–2
mol/kg Cl) fluids with maximum values of
D
Mo
∼
20,
D
B
∼
15,
D
As
∼
13,
D
Sb
∼
8,
D
Bi
∼
15 indicating dissolution as non-chloride (e.g., hydroxy) complexes. Fluid/melt partition coefficients of copper are highly variable, but highest between vapor like fluids and silicate melt (
D
Cu
⩽
2700), indicating an important role for ligands other than Cl. Partition coefficients for W generally increase with increasing chlorinity, but are exceptionally low in some of the studied brines which may indicate an effect of other parameters. Fluid/melt partition coefficients of Sn show a high variability but likely increase with the chlorinity of the fluid (
D
Sn
=
0.3–42,
D
W
=
0.8–60), and decrease with decreasing oxygen fugacity or melt peraluminosity.
We studied a unique chrysotile–antigorite serpentinite, drilled on Deep Sea Drilling Project Leg 84 (Site 566) in the Guatemala forearc. Our in situ major and trace element data provide new ...constraints on possible reactions and associated trace element mobilisation during shallow serpentinite subduction.
Chrysotile of the studied serpentinite, formed by the hydration of an upper mantle peridotite precursor, is partially replaced by antigorite (alone) which also occurs in 0.5
mm wide unoriented veins crosscutting the rock. Based on textural relationships and the P–T–X stability of the rock forming phases, the replacement of chrysotile by antigorite occurred at T
<
300
°C, due to interaction between the chrysotile–serpentinite and an aqueous fluid. A comparison of the chemical compositions of reactant and product phases reveals that about 90% of the Cl, more than 80% of the B and about 50% of the Sr hosted originally by chrysotile was lost during fluid-assisted chrysotile-to-antigorite transformation and accompanying partial dehydration, and documents the much lower affinity of antigorite for trace element uptake than that of chrysotile.
The fluid-assisted chrysotile-to-antigorite transformation and associated trace element loss documented here can occur in the shallow (<
30
km) region of subduction zones. This transformation decreases notably the Cl and B inventory of subducting serpentinites, which are regarded as one of the most important carriers of these elements into subduction zones. The evolution of serpentinites during initial subduction stages thus appears to be critical in the recycling of specific trace elements such as B or Cl from forearc to subarc depths.
► Antigorite replaced chrysotile in a serpentinite from the Guatemalan forearc. ► The mineral replacement was the result of aqueous fluid-rock interaction. ► Partial dehydration and loss of Cl, B and Sr accompanied the reaction. ► Transformation of chrysotile into antigorite may significantly reduce Cl, B and Sr inventories of serpentinites during early subduction. ► Serpentinite evolution during initial subduction stages can be critical in the recycling of B and Cl from forearc to subarc depths.
At Cima di Gagnone, garnet peridotite and chlorite harzburgite lenses within pelitic schists and gneisses correspond to eclogite-facies breakdown products of hydrated peridotites and are suitable for ...studying dehydration of serpentinized mantle. Thermobarometry and pseudosection modelling yield peak temperatures of 750-850°C and pressures <3 GPa. The minimum temperature recorded by the garnet peridotite corresponds to the maximum conditions experienced by the chlorite harzburgite, suggesting that these rocks recrystallized cofacially at ∼800°C. Alternatively, they might have decoupled during subduction, as achieved in tectonically active plate interface boundaries. The major and rare earth element (REE) variability of the peridotites was mostly acquired during pre-subduction mantle evolution as a result of partial melting and reactive melt flow. The ultramafic suite is also characterized by fluid-mobile element enrichments (B, Pb, As, Sb, Cs, Li, U, Be), which confirm derivation from variably serpentinized protoliths. Similarity in the U, Pb, B, Li and Sr contents of the Gagnone peridotites to present-day oceanic serpentinites suggests that these elements were partly taken up during initial serpentinization by seawater-derived fluids. Positive Be, As and Sb anomalies suggest involvement of fluids equilibrated with crustal (metasedimentary) reservoirs during subsequent subduction metamorphism and peridotite entrainment in (meta)sediments. Fluid-mobile element enrichment characterizes all peak eclogitic minerals, implying that multiple hydration events and element influx pre-dated the eclogite-facies dehydration. Peak anhydrous minerals retain B, Li, As and Sb concentrations exceeding primitive mantle values and may introduce geochemical anomalies into the Earth's mantle. The relatively low contents of large ion lithophile elements and light REE in the Gagnone peridotites with respect to much higher enrichments shown by metasomatized garnet peridotite pods hosted in migmatites (Ulten Zone, Eastern Alps) suggest that the crustal rocks at Gagnone did not experience partial melting. The Gagnone garnet peridotite, despite showing evidence for chlorite dehydration, retains significant amounts of fluid-mobile elements documenting that no partial melting occurred upon chlorite breakdown. We propose that the Gagnone ultramafic rocks represent a prime example of multi-stage peridotite hydration and subsequent dehydration in a plate interface setting.
The global supply of Mo and much of Cu and Au comes from porphyry-type ore deposits associated with hydrous magmas of broadly calc-alkaline composition, thought to be generated by contemporaneous ...subduction zone processes. Molybdenum is generally considered to be derived from the continental crust while Cu and Au are sourced in the mantle wedge above subducting slabs. Here we show that neither contemporaneous subduction nor derivation of Mo from crustal sources is required to explain the genesis of porphyry–Cu–Mo–Au deposits on Proterozoic lithosphere in the eastern Rocky Mountains.
Uniform Pb isotope ratios measured by LA-MC-ICP-MS in individual fluid inclusions from distinct Cu–Au and later Mo ore-forming stages at Bingham Canyon, USA, demonstrate a common metal source. Uranogenic Pb isotope ratios are particularly non-radiogenic (17.494
<
206Pb/
204Pb
<
17.534; 15.553
<
207Pb/
204Pb
<
15.588) and plot to the left of the geochron and above the mantle Pb evolution line. In
207Pb/
206Pb vs.
208Pb/
206Pb space, the fluid Pb isotope data cluster at the non-radiogenic end of a mixing line described by >
80 feldspar data from igneous rocks intimately associated with magmatic-hydrothermal ore formation, which extends to modern depleted mantle or upper crust. Forward Monte Carlo simulations require three events for the U–Th–Pb isotope evolution of the fluid: (1) Late Archean formation of enriched crust is followed by (2) preferential extraction of Pb from this aged crust into a subduction fluid characterized by drastically reduced U/Pb that metasomatized lithospheric mantle at ∼
1.8
Ga. This mantle reservoir then evolved to produce the retarded uranogenic Pb isotope signatures of the Bingham Canyon Cu–Mo–Au deposit in the Cenozoic (3).
Similarly retarded uranogenic Pb isotope data characterize the giant porphyry–Mo and Climax-type Mo deposits of Henderson, Questa, Butte, and SE Arizona that occur in Proterozoic sutures of the central and eastern Rocky Mountains. We propose that Cenozoic melting of subcontinental lithospheric mantle metasomatized by subduction fluids during early Proterozoic amalgamation of terranes to the Wyoming Craton provides the metal endowment and subduction flavour to the giant magmatic-hydrothermal Cu–Mo–Au ore deposits in western North America, which together constitute the world's major molybdenum ore province.
Recent studies report a large Mo isotope variability of up to 1‰ (expressed in δ98/95MoNIST3134) in convergent margin lavas. These isotopic variations have been associated with subduction zone ...processes and ultimately may account for heavy and variable isotope signatures in evolved continental crust. Arc lavas show both lighter and heavier Mo isotopic values when compared to the chondritic average (δ98/95MoNIST3134 −0.16 ± 0.02‰), with a concentration weighted mean isotopic composition (δ98/95MoNIST3134 +0.03‰) distinctly heavier than that of the mantle (δ98/95MoNIST3134~−0.21 to −0.16‰). The absence of isotopic fractionation during tholeiitic igneous differentiation indicates that heavy Mo isotope signatures in convergent margin rocks are intrinsic to subduction zone processes, caused either by recycling of subducted components, by Mo isotope fractionation during magmatic differentiation, or by a combination thereof. In order to gain a more detailed understanding of the Mo isotope variability in arc lavas, we have studied Mo isotopes and concentrations in calc-alkaline lavas sampled along the Banda Arc in Indonesia, an intra-oceanic subduction zone well known for variable contributions of subducting continental meterial.
Banda Arc lavas exhibit Mo isotopic compositions covering a large range from −0.48 to +0.24‰ in δ98/95MoNIST3134. We find that, combined with published data from other subduction zones, the majority of arc data are isotopically heavier compared to its presumed mantle wedge source or mid-ocean-ridge basalts. Furthermore, arc lava Mo isotope signatures show an apparent covariation between indices of amphibole-clinopyroxene fractionation from the melt. Generally, heavier Mo isotopic signatures are associated with higher degrees of REE fractionation expressed as λ1, λ2, and Dy*/Dy, high Ca/Al, and higher Sc contents. These observations can be best explained with an open system magma reservoir where fractional crystallisation, recharge and eruption are tightly linked. Notable exceptions in the Banda region are four samples with isotopically light Mo. Three of these isotopically light lavas indicate the assimilation of an isotopically light Mo reservoir with heavy δ18O and radiogenic 87Sr/86Sr-206Pb/204Pb, tentatively identified as lower arc crust. Together, our data demonstrate, in line with previous findings, that magmatic processes modify the Mo isotopic composition in arc lavas, thus adding complexity to the Mo isotope systematics inherent to subduction zones.
Molybdenum isotopes have emerged as novel tracers for high-temperature igneous and metamorphic processes. The debate remains to what extent different subducted slab lithologies, such as oceanic crust ...and marine sediments, contribute to the Mo isotope signature of arc magmas and, hence, exert different controls on the terrestrial Mo cycle. Here we investigate Mo isotope systematics from input to output at the Tongan subduction zone: Arc lavas from different Tongan islands, pelagic sediments and altered oceanic crust (AOC) samples from DSDP site 595/596 on the subducting Pacific plate. For complementary insights into the fate of Mo and its isotopic signatures during prograde subduction metamorphism, we also present data of metasediments and variably altered AOC-type eclogites from the Zermatt-Saas ophiolite, Switzerland and Italy, and the Schistes Lustrés Complex in Alpine Corsica.
Manganese oxide-rich pelagic sediments from DSDP site 595/596 show variable, depth-dependent Mo/Mn ratios and Mo isotope compositions controlled by diagenetic reactions. As subducted equivalents, Mn-rich eclogitic metapelites display lower Mo contents and δ98/95Mo ratios compared to their non-subducted protolith. This indicates prominent loss of Mo along with isotope fractionation during early subduction metamorphism. In comparison to unaltered MORB, low temperature seafloor alteration has shifted Mo/Ce and δ98/95Mo in studied AOC samples towards lower ratios, in the range of most mafic eclogites published so far. However, some mafic eclogites show even lower Mo/Ce and δ98/95Mo ratios compared to AOC, likely due to fluid-related Mo loss upon early subduction and preferential incorporation of light Mo into residual rutile.
Our data document a prominent loss of isotopically heavy Mo before and upon early subduction metamorphism at shallow depths in the forearc region. Moreover, when prograde rutile crystallizes at ~30 km depth, it fixes the largest fraction of Mo in the subducting material. This creates an “arc Mo-conundrum” as devolatization of the slab at subarc depths is not able to account for the fluid-mobile Mo source responsible for observed higher Mo/Ce and δ98/95Mo in Tongan arc lavas compared to the mantle. As an alternative scenario, Mo mobilization by slab-derived aqueous fluids during the early stages of subduction into the forearc mantle produces serpentinites enriched in Mo with a possible heavy Mo isotopic signature. Mechanical transport and devolatization of forearc serpentinites at subarc regions is a plausible alternative recycling process accounting for the observed Mo systematics in Tongan arc lavas. This is supported by positive covariations of Mo/Ce and δ98/95Mo with elements such as As, Sb, and Cs, which are thought to be mostly released from the subducting material during early stages of subduction. We propose that a multi-stage recycling of metasomatized forearc mantle can be an important process in recycling of Mo and possibly other elements.
•Mo loss and isotope fractionation occurs mainly before and during early subduction.•Rutile hosts most of the remaining light Mo in the slab already in the forearc.•Fluid signatures in Tongan arc lavas covariate with Mo/Ce and δ98/95Mo.•Subduction of metasomatized forearc mantle can explain Mo recycling in the Tongan arc.
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